U.S. patent application number 16/677800 was filed with the patent office on 2020-06-04 for endcapped polycarbonates, methods of manufacture, and articles formed therefrom.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Jordi Calveras, James Franklin Hoover, James Alan Mahood, Paul Dean Sybert.
Application Number | 20200172664 16/677800 |
Document ID | / |
Family ID | 64564723 |
Filed Date | 2020-06-04 |
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United States Patent
Application |
20200172664 |
Kind Code |
A1 |
Sybert; Paul Dean ; et
al. |
June 4, 2020 |
ENDCAPPED POLYCARBONATES, METHODS OF MANUFACTURE, AND ARTICLES
FORMED THEREFROM
Abstract
An endcapped polycarbonate, comprising thioether carbonyl
endcaps of the formula ##STR00001## wherein L is a C.sub.1-12
aliphatic or aromatic linking group, and R is a C.sub.1-20 alkyl,
C.sub.6-18 aryl, or C.sub.7-24 arylalkylene.
Inventors: |
Sybert; Paul Dean;
(Evansville, IN) ; Calveras; Jordi; (Evansville,
IN) ; Mahood; James Alan; (Evansville, IN) ;
Hoover; James Franklin; (Evansville, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
BERGEN OP ZOOM |
|
NL |
|
|
Family ID: |
64564723 |
Appl. No.: |
16/677800 |
Filed: |
November 8, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 64/14 20130101;
C08G 64/081 20130101; C08G 64/025 20130101; C08G 64/42 20130101;
C08G 64/0216 20130101; C08G 64/12 20130101; C08G 64/085 20130101;
C08G 64/24 20130101 |
International
Class: |
C08G 64/08 20060101
C08G064/08; C08G 64/12 20060101 C08G064/12 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 30, 2018 |
EP |
18209620.6 |
Claims
1. An endcapped polycarbonate comprising thioether carbonyl endcaps
of the formula ##STR00027## wherein L is a C.sub.1-12 aliphatic or
aromatic linking group, and R is a C.sub.1-20 alkyl, C.sub.6-18
aryl, or C.sub.7-24 arylalkylene.
2. The endcapped polycarbonate of claim 1, wherein the thioether
carbonyl endcaps are of the formula ##STR00028## or a combination
thereof, wherein R is a C.sub.1-20 alkyl, C.sub.6-18 aryl, or
C.sub.7-24 arylalkylene, and b is 1 to 5.
3. The endcapped polycarbonate of claim 1, wherein the thioether
carbonyl endcaps are of the formula ##STR00029## or a combination
thereof.
4. The endcapped polycarbonate of claim 1, wherein the thioether
carbonyl endcaps are present in an amount effective to provide 3 to
80 parts per million by weight of added sulfur, based on the total
parts by weight of the endcapped polycarbonate; or having a total
sulfur content of 3 to 150 parts per million by weight, based on
the total parts by weight of the endcapped polycarbonate; or
both.
5. The endcapped polycarbonate of claim 1, wherein the
polycarbonate is a homopolycarbonate, a copolycarbonate, a
poly(ester-carbonate), a poly(carbonate-siloxane), a
poly(ester-carbonate-siloxane), or a combination thereof.
6. The endcapped polycarbonate of claim 1, wherein the
polycarbonate comprises: 0 to 95 mole percent, of low heat aromatic
dihydroxy monomer groups; and 5 to 100 mole percent of high heat
aromatic dihydroxy monomer groups.
7. The endcapped polycarbonate of claim 6, wherein the low heat
aromatic dihydroxy monomer groups are bisphenol A groups, and the
high heat aromatic dihydroxy monomer groups are of the formula
##STR00030## or a combination thereof, wherein R.sup.4 is methyl or
phenyl, each R.sup.2 is methyl, and g is 1 to 4.
8. The endcapped polycarbonate of claim 1, wherein, as compared to
the same polycarbonate without the thioether carbonyl endcaps, the
endcapped polycarbonate has at least one of lower yellowness index,
lower yellowness index after heat aging, or less plate-out after
molding.
9. The endcapped polycarbonate of claim 1, wherein a molded sample
of the endcapped polycarbonate has at least one of a haze of less
than 10% as measured according to ASTM D1003-00, Procedure B,
illuminant C, on a spectrophotometer, at a thickness of 3.2 mm; or
a visible transmission of greater than or equal to 70% as
determined according to ASTM D1003-00, Procedure A, using D65
illumination, 10 degrees observer, at a thickness of 3.2 mm.
10. A method for the manufacture of the endcapped polycarbonate of
claim 1, the method comprising reacting a thioether carbonyl
endcapping agent of the formula: ##STR00031## during manufacturing
of the polycarbonate from a bisphenol, wherein G is a leaving
group, L is a C.sub.1-12 aliphatic or aromatic linking group, and R
is a C.sub.1-20 alkyl, C.sub.6-18 aryl, or C.sub.7-24
arylalkylene.
11. The method of claim 10, wherein the manufacturing is by
interfacial polymerization, and G is a hydroxy group, a salt of a
hydroxy group, or a halide.
12. The method of claim 10, wherein the manufacturing is in the
melt, and G is a hydroxy group or a salt of a hydroxy group.
13. The method of claim 10, comprising combining the thioether
carbonyl endcapping agent with the bisphenol, wherein the combining
is: during manufacturing of the bisphenol, during dissolution of
the bisphenol before manufacturing the polycarbonate, at the same
time that the bisphenol is added to a reaction mixture to form the
polycarbonate, during phosgenation to form the polycarbonate,
before shipping the bisphenol, or before storing the bisphenol.
14. (canceled)
15. An article comprising the endcapped polycarbonate of claim
1.
16. The article of claim 15, wherein the article is a molded
article, an extruded layer, or an extruded fiber.
17. The article of claim 15, wherein the article is a lens that is
optionally hardcoated.
18. The article of claim 15, prepared by injection molding or
extruding the endcapped polycarbonate.
19. The endcapped polycarbonate of claim 7, wherein the high heat
aromatic dihydroxy monomer groups are of the formula ##STR00032##
or a combination thereof.
20. The endcapped polycarbonate of claim 1, wherein the thioether
carbonyl endcaps are present in an amount effective to provide 3 to
70 parts per million by weight of added sulfur, based on the total
parts by weight of the endcapped polycarbonate; or having a total
sulfur content of 3 to 100 parts per million by weight, based on
the total parts by weight of the endcapped polycarbonate; or
both.
21. The endcapped polycarbonate of claim 6, wherein the
polycarbonate comprises: 5 to 90 mole percent of the low heat
aromatic dihydroxy monomer groups; and 10 to 95 mole percent of the
high heat aromatic dihydroxy monomer groups.
Description
BACKGROUND
[0001] This disclosure is directed to endcapped polycarbonates,
compositions including the endcapped polycarbonates, articles
formed therefrom, and their methods of manufacture.
[0002] Polycarbonates are useful in the manufacture of articles and
components for a wide range of applications, from automotive parts
to electronic appliances. Because of their broad use, particularly
in automotive, lighting, and consumer electronics industries, it is
desirable to provide polycarbonates with improved low color and
color stability with heat aging. It would be a further advantage if
the polycarbonates had good molding properties. As is known in the
art, polycarbonates can be subject to increased color with molding.
Use of higher levels of mold release agents to improve mold release
can lead to plate out of the release agent in the molds. It would
be a still further advantage if these properties could be obtained
in polycarbonates with high thermal resistance, for example from
100 to 150.degree. C., or higher.
SUMMARY
[0003] An endcapped polycarbonate comprises thioether carbonyl
endcaps of the formula --C(.dbd.O)-L-S--R, wherein L is a
C.sub.1-12 aliphatic or aromatic linking group, R is a C.sub.1-20
alkyl, C.sub.6-18 aryl, or C.sub.7-24 arylalkylene.
[0004] A method for the manufacture of the endcapped polycarbonate
comprises reacting a thioether carbonyl endcapping agent of the
formula: G-C(.dbd.O)-L-S--R during manufacturing the polycarbonate
from a bisphenol, wherein G is a leaving group, L is a C.sub.1-12
aliphatic or aromatic linking group, and R is a C.sub.1-20 alkyl,
C.sub.6-18 aryl, or C.sub.7-24 arylalkylene.
[0005] A method of manufacturing an article that comprises the
endcapped polycarbonate is disclosed, preferably wherein the
manufacturing comprises injection molding or extruding the
endcapped polycarbonate.
[0006] An article comprises the endcapped polycarbonate, preferably
wherein the article is a molded article, an extruded layer, or an
extruded fiber. In an aspect, the article can be an optical article
such as a lens.
[0007] The above described and other features are exemplified by
the following drawings, detailed description, examples, and
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The following is a brief description of the drawings which
are exemplary.
[0009] FIG. 1 is a graph showing polycarbonate color as a function
of thioether carbonyl endcap concentration under two different
temperature/time conditions.
[0010] FIG. 2 is a graph showing color as a function of barrel
temperature for a control and a polycarbonate containing 30 parts
per million by weight (ppm) of sulfur.
DETAILED DESCRIPTION
[0011] Polycarbonates having sulfur-containing endcaps, and in
particular thioether carbonyl endcaps, are described herein. It has
been unexpectedly found that such endcaps can provide
polycarbonates that have improved properties, including one or more
of low color (e.g., low yellowness index) during manufacture and
improved color stability with heat aging. The polycarbonates can
accordingly provide improved color for articles that are extruded,
molded, or otherwise processed in the melt. The high temperature
color stability also extends to the use of the article. These
results are particularly unexpected in view of the teaching of U.S.
Pat. No. 9,868,817 B2, which discloses that the presence of sulfur
in polycarbonates adversely impacts color and color stability, and
JP 2006-028391 (02-02-2006), which discloses that low sulfur
content in polycarbonates is important to obtain low color even in
high heat polycarbonates.
[0012] The thioether carbonyl endcaps can be incorporated into high
heat polycarbonates intended for use in high heat applications
where color stability is difficult to achieve. For example, the
thioether carbonyl endcaps can be used without significant loss of
modulus, impact resistance, transmission, haze, chemical
resistance, and ageing resistance.
[0013] In another unexpected feature, it has been found that the
presence of the thioether carbonyl endcaps, and in particular those
including C.sub.6-14 alkyl substituents, provides improved mold
release properties. Compositions including polycarbonates having
the thioether carbonyl endcaps can be processed with less added
mold release agent and therefore can have improved resistance to
plate-out during injection molding, film extrusion, fiber
extrusion, and the like.
[0014] The thioether endcaps can be derived from a
sulfur-containing endcapping agent, and in particular can be a
thioether carbonyl compound of formula (A)
##STR00002##
wherein G is leaving group, L is a C.sub.1-12 aliphatic or aromatic
linking group, and R is a C.sub.1-20 alkyl, C.sub.6-18 aryl, or
C.sub.7-24 alkylarylene, preferably a C.sub.1-14 alkyl, C.sub.6-12
aryl, or a C.sub.7-13 arylalkylene. Preferably R is a C.sub.6-14
alkyl. For example, G can be a halide, a hydroxy group (--OH), or a
salt of a hydroxy group. For example, the salt can be an alkali
metal or alkaline-earth metal salt, an ammonium salt, or the like.
In another aspect, G of formula (A) can be of the formula
--OR.sup.a and the thioether carbonyl compound can be of formula
(A1)
##STR00003##
wherein R.sup.a is a C.sub.1-3 alkyl, C.sub.6-18 aryl, C.sub.7-24
alkylarylene, or C.sub.7-24 arylalkylene, and L and R are as
defined in formula (A), preferably wherein R is a C.sub.6-14
alkyl.
[0015] The endcapping agent can be a thioether carbonyl compound
(A2) or (A3):
##STR00004##
wherein R is a C.sub.1-20 alkyl, C.sub.6-18 aryl, or C.sub.7-24
arylalkylene, preferably a C.sub.1-14 alkyl, C.sub.6-12 aryl, or a
C.sub.7-13 arylalkylene, b is 1 to 5, preferably 1 to 2, and G is
as defined in formula (A). In an aspect R is C.sub.6-14 alkyl, b is
1 to 5, preferably 1 to 2, and G is R.sup.a as defined in formula
A1, preferably sC.sub.1-3 alkyl.
[0016] For example, the endcapping agent can be a thioether
carbonyl compound of formulas (B1) to (B5)
##STR00005##
[0017] or a combination thereof.
[0018] The sulfur-containing endcapping agent can be used alone or
in combination with other endcapping agents. More than one
sulfur-containing endcapping agent can be used, such as 2, 3, or 4
or more different sulfur-containing endcapping agents.
[0019] The polycarbonates accordingly comprise thioether carbonyl
endcaps of the formula --C(.dbd.O)-L-S--R, wherein L is a
C.sub.1-12 aliphatic or aromatic linking group and R is a
C.sub.1-20 alkyl, C.sub.6-18 aryl, or C.sub.7-24 arylalkylene. The
endcaps can be of the formula
##STR00006##
or a combination thereof, wherein R is a C.sub.1-20 alkyl,
C.sub.6-18 aryl, or C.sub.7-24 arylalkylene, preferably a
C.sub.1-14 alkyl, C.sub.6-12 aryl, or a C.sub.7-13 arylalkylene,
and b is 1-5, preferably 1-2.
[0020] In another preferred aspect, the thioether carbonyl endcaps
are of the formula
##STR00007##
or a combination thereof.
[0021] "Polycarbonate" as used herein means a homopolycarbonate,
copolycarbonate, or polycarbonate copolymer having repeating
structural carbonate units of formula (1)
##STR00008##
wherein at least 60 percent of the total number of R.sup.1 groups
are aromatic, or each R.sup.1 contains at least one C.sub.6-30
aromatic group. Specifically, each R.sup.1 can be derived from a
dihydroxy compound such as an aromatic dihydroxy compound of
formula (2) or a bisphenol of formula (3):
##STR00009##
wherein each R.sup.h is independently a halogen atom, for example
bromine, a C.sub.1-10 hydrocarbyl group such as a C.sub.1-10 alkyl,
a halogen-substituted C.sub.1-10 alkyl, a C.sub.6-10 aryl, or a
halogen-substituted C.sub.6-10 aryl, and n is 0 to 4.
[0022] In formula (3), R.sup.a and R.sup.b are each independently a
halogen, C.sub.1-12 alkoxy, or C.sub.1-12 alkyl, and p and q are
each independently integers of 0 to 4, such that when p or q is
less than 4, the valence of each carbon of the ring is filled by
hydrogen. For example, p and q can be 0, or p and q can be 1, and
R.sup.a and R.sup.b can each be a C.sub.1-3 alkyl group,
specifically methyl, disposed meta to the hydroxy group on each
arylene group. X.sup.a is a bridging group connecting the two
hydroxy-substituted aromatic groups, where the bridging group and
the hydroxy substituent of each C.sub.6 arylene group are disposed
ortho, meta, or para (specifically para) to each other on the
C.sub.6 arylene group, for example, a single bond, --O--, --S--,
--S(O)--, --S(O).sub.2--, --C(O)--, or a C.sub.1-18 organic group,
which can be cyclic or acyclic, aromatic or non-aromatic, and can
further comprise heteroatoms such as halogens, oxygen, nitrogen,
sulfur, silicon, or phosphorous. For example, Xa can be a
substituted or unsubstituted C.sub.3-18 cycloalkylidene; a
C.sub.1-25 alkylidene of the formula --C(R.sup.c)(R.sup.d)--
wherein R.sup.c and R.sup.d are each independently hydrogen,
C.sub.1-12 alkyl, C.sub.1-12 cycloalkyl, C.sub.7-12 arylalkyl,
C.sub.1-12 heteroalkyl, or cyclic C.sub.7-12 heteroarylalkyl; or a
group of the formula --C(.dbd.R.sup.e)-- wherein R.sup.e is a
divalent C.sub.1-12 hydrocarbon group.
[0023] Polycarbonates and their methods of manufacture are known in
the art, being described, for example, in WO 2013/175448 A1, US
2014/0295363, and WO 2014/072923. Examples of bisphenol compounds
are described therein, and include, but are not limited to,
Specific dihydroxy compounds include resorcinol,
2,2-bis(4-hydroxyphenyl) propane ("bisphenol A" or "BPA"),
3,3-bis(4-hydroxyphenyl) phthalimidine,
2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine (also known as
N-phenyl phenolphthalein bisphenol, "PPPBP", or
3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one),
1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (isophorone
bisphenol).
[0024] Preferably, the bisphenol is substantially free of halogen
substituents. For example, the bisphenol can have less than 100
ppm, more preferably less than 50 ppm, and even more preferably
less than 5 ppm of chlorine, bromine, and iodine.
[0025] The polycarbonate can be a high heat polycarbonate. The high
heat polycarbonates comprise high heat aromatic dihydroxy monomer
groups as described in more detail below. The high heat
polycarbonates can comprise only high heat aromatic dihydroxy
monomer groups, but more commonly are copolycarbonates comprising a
combination of low heat aromatic dihydroxy monomer groups and high
heat aromatic dihydroxy monomer groups.
[0026] The low heat aromatic dihydroxy monomer groups are derived
from a low heat aromatic dihydroxy monomer of formula (3) and have
from 12 to 18 carbon atoms. As used herein, a "low heat aromatic
dihydroxy monomer" means a compound that can be used to manufacture
a polycarbonate homopolymer having a Tg of less than 170.degree.
C., for example 120-160.degree. C., each as determined by
differential scanning calorimetry (DSC) as per ASTM D3418 with a
20.degree. C./min heating rate. A preferred low heat dihydroxy
monomer is bisphenol A.
[0027] The high heat aromatic dihydroxy monomer groups include
specific monomers having 19 or more carbon atoms. Thus, in formula
(1), each R.sup.1 is independently (a) a C.sub.12-18 low heat
divalent bisphenol group or (b) a C.sub.19 or higher divalent
bisphenol group derived from a high heat monomer as further
described below. In an aspect, each R.sup.1 independently consists
essentially, or consist of, (a) a bisphenol A divalent group and
(b) the C.sub.19 or higher divalent group derived from a high heat
monomer.
[0028] The high heat aromatic dihydroxy monomer group is derived
from a high heat aromatic dihydroxy monomer having at least 19
carbon atoms. As used herein, a high heat aromatic dihydroxy
monomer is a monomer where the corresponding homopolycarbonate of
the monomer has a glass transition temperature (Tg) of 170.degree.
C. or higher, for example a Tg of 175-330.degree. C., each
determined by differential scanning calorimetry (DSC) as per ASTM
D3418 with a 20.degree. C./min heating rate. Examples of such high
heat aromatic dihydroxy monomer groups include groups of formulas
(4) to (10)
##STR00010## ##STR00011##
wherein R.sup.c and R.sup.d are each independently a C.sub.1-12
alkyl, C.sub.2-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.f is hydrogen or both Rf together are a carbonyl
group, each R.sup.3 is independently C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.1-6 alkyl, or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, R.sup.6 is independently C.sub.1-3
alkyl, or phenyl, preferably methyl, X.sup.a is a C.sub.6-12
polycyclic aryl, C.sub.3-18 mono- or polycycloalkylene, C.sub.3-18
mono- or polycycloalkylidene, --C(R.sup.f)(R.sup.g)-- wherein
R.sup.f is hydrogen, C.sub.1-12 alkyl, or C.sub.6-12 aryl and
R.sup.g is C.sub.6-10 alkyl, C.sub.6-8 cycloalkyl, or C.sub.6-12
aryl, or -(Q.sup.a).sub.x-G-(Q.sup.b).sub.y-group, wherein Q.sup.a
and Q.sup.b are each independently a C.sub.1-3 alkylene, G is a
C.sub.3-10 cycloalkylene, x is 0 or 1, and y is 0 or 1, and j, m,
and n are each independently 0 to 4. A combination of high heat
aromatic dihydroxy monomer groups can be used.
[0029] For example, R.sup.c and R.sup.d can be each independently a
C.sub.1-3 alkyl, or C.sub.1-3 alkoxy, each R.sup.6 can be methyl,
each R.sup.3 can be independently C.sub.1-3 alkyl, R.sup.4 can be
methyl, or phenyl, each R.sup.6 can be independently C.sub.1-3
alkyl, or phenyl, preferably methyl, X.sup.a can be a C.sub.6-12
polycyclic aryl, C.sub.3-18 mono- or polycycloalkylene, C.sub.3-18
mono- or polycycloalkylidene, --C(R.sup.f)(R.sup.g)-- wherein
R.sup.f can be hydrogen, C.sub.1-12 alkyl, or C.sub.6-12 aryl, and
R.sup.g can be C.sub.6-10 alkyl, C.sub.6-8 cycloalkyl, or
C.sub.6-12 aryl, or -(Q.sup.1).sub.x-G-(Q.sup.2).sub.y-group,
wherein Q.sup.1 and Q.sup.2 can each independently be a C.sub.1-3
alkylene and G can be a C.sub.3-10 cycloalkylene, x can be 0 or 1,
and y can be 0 or 1, and j, m, and n can each independently be 0 or
1.
[0030] Exemplary high heat aromatic dihydroxy monomer groups
include those of formulas (5a), (6a), (9a), and (10a) to (10l)
##STR00012## ##STR00013## ##STR00014##
wherein R.sup.c and R.sup.d are the same as defined for formulas
(4) to (10), each R.sup.2 is independently C.sub.1-4 alkyl, m and n
are each independently 0 to 4, each R.sup.3 is independently
C.sub.1-4 alkyl or hydrogen, R.sup.4 is C.sub.1-6 alkyl or phenyl
optionally substituted with 1 to 5 C.sub.1-6 alkyl groups, and g is
0 to 10. In a specific aspect each bond of the bisphenol group is
located para to the linking group that is X.sup.a. In an aspect,
R.sup.c and R.sup.d are each independently a C.sub.1-3 alkyl, or
C.sub.1-3 alkoxy, each R.sup.2 is methyl, x is 0 or 1, y is 1, and
m and n are each independently 0 or 1.
[0031] The high heat aromatic dihydroxy monomer group is preferably
of formula (9a-2) or (10a-2)
##STR00015##
wherein R.sup.4 is methyl or phenyl, each R.sup.2 is methyl, and g
is 1 to 4.
[0032] Preferably, the high heat aromatic group is derived from the
corresponding bisphenol, in particular from
3,8-dihydroxy-5a,10b-diphenyl-coumarano-2',3',2,3-coumarane,
4,4'-(3,3-dimethyl-2,2-dihydro-1H-indene-1,1-diyl)diphenol ,
2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine (PPPBP),
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,
4,4'-(1-phenylethylidene)bisphenol,
9,9-bis(4-hydroxyphenyl)fluorene,
1,1-bis(4-hydroxyphenyl)cyclododecane, or a combination thereof.
More preferably, the high heat aromatic dihydroxy monomer group is
derived from PPPBP, BPI, or a combination thereof.
##STR00016##
[0033] The C.sub.19 or higher divalent group is present in an
amount of 5 to 100 mol %, preferably 10 to 95 mol %, more
preferably 20 to 85 mol %, based on the total moles of the
bisphenol groups in the endcapped polycarbonate. The low heat
aromatic dihydroxy monomer groups are present in an amount of 0 to
95 mol %, preferably 5 to 90 mol %, more preferably 15 to 80 mol %,
based on the total moles of the bisphenol groups in the endcapped
polycarbonate. In an aspect the, the high heat carbonate group is
derived from PPPBP, BPI, or a combination thereof, and the low
carbonate group is derived from bisphenol A.
[0034] In contrast to the teachings of the prior art, the inventors
have found that polycarbonates containing sulfur can have improved
properties such as transparency, provided that the source of the
sulfur is present in the endcapping agents as described herein.
This sulfur is referred to herein as "added sulfur", and excludes
any contaminant sulfur present in the components used in the
manufacture of the copolycarbonates, i.e., the high heat aromatic
dihydroxy monomer, the low heat aromatic dihydroxy monomer, and the
carbonate source, for example. Nonetheless, it can be advantageous
to minimize or eliminate contaminant sulfur from these sources.
Accordingly, in an aspect the high heat aromatic dihydroxy monomer
and the low heat aromatic dihydroxy monomer each have a sulfur
content of less than 5 parts per million by weight (ppm) based on
the parts by weight of the polycarbonate. In another aspect, the
low heat aromatic dihydroxy monomer and the high heat aromatic
dihydroxy monomer each have a purity of at least 99.6%, at least
99.7%, or at least 99.8% as determined by HPLC and a sulfur content
of less than 5 ppm based on the parts by weight of the
polycarbonate. In a preferred aspect, the low heat aromatic
dihydroxy monomer and the high heat aromatic dihydroxy monomer each
can have a purity of at least 99.8% and a sulfur content of less
than 5 ppm based on the parts by weight of the polycarbonate.
[0035] As stated above, "polycarbonates" includes
homopolycarbonates (wherein each R.sup.1 in the polymer is the
same). "Copolycarbonates" include copolymers comprising at least
two different R.sup.1 moieties in the carbonate units, and
polycarbonate copolymers comprise carbonate units and other types
of polymer units, such as ester units or siloxane units (e.g.,
polycarbonate polysiloxane copolymers, polyester-polycarbonates,
isosorbide-containing polycarbonates).
[0036] A specific type of polycarbonate copolymer is a
poly(ester-carbonate), also known as a polyester-polycarbonate.
Poly(ester-carbonate)s further contain, in addition to recurring
carbonate chain units of formula (1), repeating ester units of
formula (11)
##STR00017##
wherein J is a divalent group derived from a dihydroxy compound
(which includes a reactive derivative thereof), and can be, for
example, a C.sub.1-10 alkylene, a C.sub.6-20 cycloalkylene, a
C.sub.5-20 arylene, or a polyoxyalkylene group in which the
alkylene groups contain 2 to 6 carbon atoms, specifically, 2, 3, or
4 carbon atoms; and T is a divalent group derived from a
dicarboxylic acid (which includes a reactive derivative thereof),
and can be, for example, a C.sub.1-20 alkylene, a C.sub.5-20
cycloalkylene, or a C.sub.6-20 arylene. Copolyesters containing a
combination of different T or J groups can be used. The polyester
units can be branched or linear.
[0037] Specific dihydroxy compounds include aromatic dihydroxy
compounds of formula (2) (e.g., resorcinol), bisphenols of formula
(3) (e.g., bisphenol A), a C.sub.1-8 aliphatic diol such as ethane
diol, n-propane diol, i-propane diol, 1,4-butane diol,
1,4-cyclohexane diol, 1,4-hydroxymethylcyclohexane, or a
combination thereof. Aliphatic dicarboxylic acids that can be used
include C.sub.5-20 aliphatic dicarboxylic acids (which includes the
terminal carboxyl groups), specifically linear C.sub.8-12 aliphatic
dicarboxylic acid such as decanedioic acid (sebacic acid); and
alpha, omega-C.sub.12 dicarboxylic acids such as dodecanedioic acid
(DDDA). Aromatic dicarboxylic acids that can be used include
terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,
1,4-cyclohexane dicarboxylic acid, or a combination thereof. A
combination of isophthalic acid and terephthalic acid wherein the
weight ratio of isophthalic acid to terephthalic acid is 91:9 to
2:98 can be used.
[0038] Specific ester units include ethylene terephthalate units,
n-propylene terephthalate units, n-butylene terephthalate units,
ester units derived from isophthalic acid, terephthalic acid, and
resorcinol (ITR ester units), and ester units derived from sebacic
acid and bisphenol A. The molar ratio of ester units to carbonate
units in the poly(ester-carbonate)s can vary broadly, for example
1:99 to 99:1, specifically, 10:90 to 90:10, more specifically,
25:75 to 75:25, or from 2:98 to 15:85. The molar ratio of ester
units to carbonate units in the poly(ester-carbonate)s can vary
from 1:99 to 30: 70, specifically 2:98 to 25:75, more specifically
3:97 to 20:80, or from 5:95 to 15:85.
[0039] The endcapped polycarbonate copolymer can be a
poly(carbonate-siloxane), also referred to in the art as a
polycarbonate-polysiloxane copolymer. The polysiloxane blocks
comprise repeating diorganosiloxane units as in formula (12)
##STR00018##
wherein each R is independently a C.sub.1-13 monovalent organic
group. For example, R can be a C.sub.1-13 alkyl, C.sub.1-13 alkoxy,
C.sub.2-13 alkenyl, C.sub.2-13 alkenyloxy, C.sub.3-6 cycloalkyl,
C.sub.3-6 cycloalkoxy, C.sub.6-14 aryl, C.sub.6-10 aryloxy,
C.sub.7-13 arylalkyl, C.sub.7-13 arylalkyleneoxy, C.sub.7-13
alkylarylene, or C.sub.7-13 alkylaryleneoxy. The foregoing groups
can be fully or partially halogenated with fluorine, chlorine,
bromine, or iodine, or a combination thereof. Where a transparent
poly(carbonate-siloxane) is desired, R can be unsubstituted by
halogen. Combinations of the foregoing R groups can be used in the
same copolymer.
[0040] The value of E in formula (12) can vary widely depending on
the type and relative amount of each component in the thermoplastic
composition, the desired properties of the composition, and like
considerations. Generally, E has an average value of 2 to 1,000,
specifically 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70.
For example, E can have an average value of 10 to 80 or 10 to 40,
or E can have an average value of 40 to 80, or 40 to 70. Where E is
of a lower value, e.g., less than 40, it can be desirable to use a
relatively larger amount of the poly(carbonate-siloxane) copolymer.
Conversely, where E is of a higher value, e.g., greater than 40, a
relatively lower amount of the poly(carbonate-siloxane) copolymer
can be used.
[0041] The polysiloxane blocks can be of formula (13)
##STR00019##
wherein E and R are as defined in formula (12) and Ar can be the
same or different, and is a substituted or unsubstituted C.sub.6-30
arylene, wherein the bonds are directly connected to an aromatic
moiety. Ar groups in formula (13) can be derived from a C.sub.6-30
dihydroxyarylene compound, for example a dihydroxyarylene compound
of formula (3) or (6) above. Dihydroxyarylene compounds include
1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane,
2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane,
2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane,
1,1-bis(4-hydroxyphenyl) n-butane,
2,2-bis(4-hydroxy-l-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)
cyclohexane, bis(4-hydroxyphenyl sulfide),
1,1-bis(4-hydroxy-t-butylphenyl) propane, or a combination
thereof.
[0042] The polysiloxane blocks can be of formula (14)
##STR00020##
wherein R and E are as described above, and each R.sup.5 is
independently a divalent C.sub.1-30 organic group, and wherein the
polymerized polysiloxane unit is the reaction residue of its
corresponding dihydroxy compound. For example, the polysiloxane
blocks can be of formula (15):
##STR00021##
wherein R and E are as defined in formula (12). R.sup.6 in formula
(14) is a divalent C.sub.2-8 aliphatic. Each M in formula (15) can
be the same or different, and can be a halogen, cyano, nitro,
C.sub.1-8 alkylthio, C.sub.1-8 alkyl, C.sub.1-8 alkoxy, C.sub.2-8
alkenyl, C.sub.2-8 alkenyloxy, C.sub.3-8 cycloalkyl, C.sub.3-8
cycloalkoxy, C.sub.6-10 aryl, C.sub.6-10 aryloxy, C.sub.7-12
aralkyl, C.sub.7-12 arylalkyleneoxy, C.sub.7-12 alkylarylene, or
C.sub.7-12 alkylaryleneoxy, wherein each n is independently 0, 1,
2, 3, or 4.
[0043] In Formula (15), M is bromo or chloro, an alkyl such as
methyl, ethyl, or propyl, an alkoxy such as methoxy, ethoxy, or
propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl; R.sup.6
is a dimethylene, trimethylene or tetramethylene; and R is a
C.sub.1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or
aryl such as phenyl, chlorophenyl or tolyl. In another example, R
is methyl, or a combination of methyl and trifluoropropyl, or a
combination of methyl and phenyl. In still another example, R is
methyl, M is methoxy, n is one, and R6 is a divalent C.sub.1-3
aliphatic group. Specific polysiloxane blocks can be of the
formula
##STR00022##
or a combination thereof, wherein E can have an average value of 2
to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to
20.
[0044] Blocks of formula (15) can be derived from the corresponding
dihydroxy polysiloxane, which in turn can be prepared effecting a
platinum-catalyzed addition between the siloxane hydride and an
aliphatically unsaturated monohydric phenol such as eugenol,
2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
4-allyl-2-bromophenol, 4-allyl-2-t -butoxyphenol,
4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol,
2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol,
2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol.
The poly(carbonate-siloxane) copolymers can then be manufactured,
for example, by the synthetic procedure of European Patent
Application Publication No. 0 524 731 A1 of Hoover, page 5,
Preparation 2.
[0045] Transparent poly(carbonate-siloxane) copolymers comprise
carbonate units (1) derived from bisphenol A, and repeating
siloxane units (14a), (14b), (14c), or a combination thereof
(specifically of formula 14a), wherein E has an average value of 4
to 50, 4 to 15, specifically 5 to 15, more specifically 6 to 15,
and still more specifically 7 to 10. The transparent copolymers can
be manufactured using one or both of the tube reactor processes
described in U.S. 2004/0039145A1 or the process described in U.S.
Pat. No. 6,723,864 can be used to synthesize the
poly(carbonate-siloxane) copolymers.
[0046] The poly(carbonate-siloxane) copolymers can comprise 50 to
99 weight percent (wt %) of carbonate units and 1 to 50 wt %
siloxane units. Within this range, the siloxane-polycarbonate
copolymer can comprise 70 to 98 wt %, more specifically 75 to 97 wt
% of carbonate units and 2 to 30 wt %, more specifically 3 to 25 wt
% siloxane units.
[0047] The copolycarbonate can be prepared from substantially pure
starting materials. The low heat aromatic dihydroxy monomer, the
high heat aromatic dihydroxy monomer, and the siloxane each can
have a purity of at least 99.6%, at least 99.7%, or at least 99.8%
as determined by high performance liquid chromatography (HPLC). In
an aspect, the high heat aromatic dihydroxy monomer can have a
purity of 99.8% or greater. In an aspect, the low heat aromatic
dihydroxy monomer can have a purity of 99.8% or greater. In an
aspect, the siloxane monomers can have a purity of 99.8% or
greater. In a preferred aspect, the high heat aromatic dihydroxy
monomer and the low heat aromatic dihydroxy monomer each can have a
purity of 99.8% or greater.
[0048] The polycarbonates can be manufactured by processes such as
interfacial polymerization and melt polymerization. High Tg
copolycarbonates are generally manufactured using interfacial
polymerization. Although the reaction conditions for interfacial
polymerization can vary, an exemplary process generally involves
dissolving or dispersing a dihydroxy compound in aqueous NaOH or
KOH, adding the resulting mixture to a water-immiscible solvent,
and contacting the reactants with a carbonate precursor in the
presence of a catalyst such as, for example, a tertiary amine or a
phase transfer catalyst, under controlled pH conditions, e.g., 8 to
10.
[0049] The aqueous NaOH or KOH preferably contains less than 20 ppm
of chlorates. WO 2017/037637 A1 discloses the chlorination of the
monomers and/or polymer backbone by chlorate during the interfacial
polymerization process, resulting in increased color and decreased
color stability. Preferably, the aqueous NaOH or KOH is
substantially free of metal ions, for example containing less than
2 ppm of iron.
[0050] The water-immiscible solvent can be, for example, methylene
chloride, 1,2-dichloroethane, chlorobenzene, toluene, or the
like.
[0051] Exemplary carbonate precursors include a carbonyl halide
such as carbonyl bromide or carbonyl chloride (phosgene) a
bishaloformate of a dihydroxy compound (e.g., the bischloroformate
of bisphenol A, hydroquinone ethylene glycol, neopentyl glycol, or
the like), and diaryl carbonates. Combinations of carbonate
precursors can also be used. The diaryl carbonate ester can be
diphenyl carbonate, or an activated diphenyl carbonate having
electron-withdrawing substituents on each aryl, such as
bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,
bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate,
bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl)
carboxylate, bis(4-acetylphenyl) carboxylate, or a combination
thereof.
[0052] In the manufacture of poly(ester-carbonate)s by interfacial
polymerization, rather than using the dicarboxylic acid or diol
directly, the reactive derivatives of the diacid or diol, such as
the corresponding acid halides, in particular the acid dichlorides
and the acid dibromides can be used. Thus, for example instead of
using isophthalic acid, terephthalic acid, or a combination
thereof, isophthaloyl dichloride, terephthaloyl dichloride, or a
combination thereof can be used.
[0053] Among tertiary amines that can be used as catalysts in
interfacial polymerization are aliphatic tertiary amines such as
triethylamine and tributylamine, cycloaliphatic tertiary amines
such as N,N-diethyl-cyclohexylamine, and aromatic tertiary amines
such as N,N-dimethylaniline. Among the phase transfer catalysts
that can be used are catalysts of the formula
(R.sup.3).sub.4Q.sup.+X, wherein each R.sup.3 is the same or
different, and is a C.sub.1-10 alkyl; Q is a nitrogen or phosphorus
atom; and X is a halogen atom or a C.sub.1-8 alkoxy or C.sub.6-18
aryloxy. Exemplary phase transfer catalysts include
(CH.sub.3(CH.sub.2).sub.3).sub.4NX,
(CH.sub.3(CH.sub.2).sub.3).sub.4PX,
(CH.sub.3(CH.sub.2).sub.5).sub.4NX,
(CH.sub.3(CH.sub.2).sub.6).sub.4NX,
(CH.sub.3(CH.sub.2).sub.4).sub.4NX,
CH.sub.3(CH.sub.3(CH.sub.2).sub.3).sub.3NX, and
CH.sub.3(CH.sub.3(CH.sub.2).sub.2).sub.3NX, wherein X is Cl.sup.-,
Br.sup.-, a C.sub.1-8 alkoxy or a C.sub.6-18 aryloxy. An effective
amount of a phase transfer catalyst can be 0.1 to 10 wt %, or 0.5
to 2 wt %, each based on the weight of dihydroxy compound in the
phosgenation mixture.
[0054] Alternatively, melt processes can be used to make the
polycarbonates. In the melt polymerization process, polycarbonates
or polycarbonate copolymers can generally be prepared by
co-reacting, in a molten state, a dihydroxy reactant as described
above and a diaryl carbonate ester as described above in the
presence of a transesterification catalyst. Conditions for melt
process are described, for example, in WO2013/027165 and the
references cited therein. Catalysts used in the melt polymerization
can include an alpha catalyst and a beta catalyst. Alpha catalysts
can comprise a source of alkali or alkaline earth ions and are
typically more thermally stable and less volatile than beta
catalysts. Beta catalysts are typically volatile and degrade at
elevated temperatures and can comprise a tranesterification
catalyst of the formula (R.sup.3).sub.4Q.sup.+X as described above.
Beta catalysts are therefore preferred for use at early
low-temperature polymerization stages. The alpha catalyst can be
used in an amount sufficient to provide 1.times.10.sup.-2 to
1.times.10.sup.-8 moles, specifically, 1.times.10.sup.-4 to
1.times.10.sup.-7 moles of metal per mole of the dihydroxy
compounds used. The amount of beta catalyst (e.g., organic ammonium
or phosphonium salts) can be 1.times.10.sup.-2 to
1.times.10.sup.-5, specifically 1.times.10.sup.-3 to
1.times.10.sup.-4 moles per total mole of the dihydroxy compounds
in the reaction mixture. Quenching of the transesterification
catalysts and any reactive catalysts residues with an acidic
compound after polymerization is completed can also be useful in
some melt polymerization processes. Among the many quenchers that
can be used are alkyl sulfonic esters of the formula
R.sup.8SO.sub.3R.sup.9 wherein R.sup.8 is hydrogen, C.sub.1-12
alkyl, C.sub.6-18 aryl, or C.sub.7-19 alkylarylene, and R.sup.9 is
C.sub.1-12 alkyl, C.sub.6-18 aryl, or C.sub.7-19 alkylarylene
(e.g., benzenesulfonate, p-toluenesulfonate, methylbenzene
sulfonate, ethylbenzene sulfonate, n-butyl benzenesulfonate, octyl
benzenesulfonate and phenyl benzenesulfonate, methyl
p-toluenesulfonate, ethyl p-toluenesulfonate, n-butyl p-toluene
sulfonate, octyl p-toluenesulfonate and phenyl p-toluenesulfonate,
in particular alkyl tosylates such as n-butyl tosylate).
[0055] As described above, the thioether carbonyl endcapping agent
is included during polymerization to provide at least a portion of
the end groups to an endcapped polycarbonate. For example, the
thioether carbonyl endcapping agent is reacted during manufacturing
the polycarbonate from a bisphenol. The thioether carbonyl
endcapping agent can be combined with the bisphenol during
manufacturing the bisphenol, before storing the bisphenol, before
transporting the bisphenol, during dissolution of the bisphenol in
a solvent or basic solution before manufacturing the polycarbonate,
at the same time that the bisphenol is added to a reaction mixture
to form the polycarbonate, or during phosgenation to form the
polycarbonate. Branched polycarbonate blocks can be prepared by
adding a branching agent during polymerization. These branching
agents include polyfunctional organic compounds containing at least
three functional groups selected from hydroxyl, carboxyl,
carboxylic anhydride, haloformyl, and mixtures of the foregoing
functional groups. Specific examples include trimellitic acid,
trimellitic anhydride, trimellitic trichloride,
tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
and benzophenone tetracarboxylic acid. The branching agents can be
added at a level of 0.05 to 2.0 wt %. Combinations comprising
linear polycarbonates and branched polycarbonates can be used.
[0056] The thioether carbonyl endcaps can be incorporated into the
endcapped polycarbonate in an amount effective for the thioether
carbonyl endcaps to provide 3 to 80 ppm, or 3 to 70, or 5 to 70
ppm, preferably 5 to 50 ppm, more preferably 10 to 50 ppm of added
sulfur, each based on the total parts by weight of the endcapped
polycarbonate. In some aspects the endcapped polycarbonate can have
a total sulfur content of 3 to 150 ppm, or 3 to 100 ppm, preferably
5 to 100 ppm, or 3 to 70 ppm, or 5 to 50 ppm, more preferably 10 to
50 ppm, each based on the total parts by weight of the endcapped
polycarbonate. For example, the total sulfur content can be 3 to 50
ppm, or 5 to 50 ppm. The total sulfur content can be measured as
provided below and includes the amount of sulfur from the thioether
carbonyl endcaps and other sources (e.g., starting materials,
solvents, byproducts, or the like.
[0057] Additional endcapping agents can be included, for example
monocyclic phenols such as phenol and C.sub.1-22 alkyl-substituted
phenols such as p-cumyl-phenol (PCP), resorcinol monobenzoate, and
p-and tertiary-butyl phenol, monoethers of diphenols, such as
p-methoxyphenol, and alkyl-substituted phenols with branched chain
alkyl substituents having 8 to 9 carbon atoms,
4-substituted-2-hydroxybenzophenones and their derivatives, aryl
salicylates, monoesters of diphenols such as resorcinol
monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their
derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their
derivatives, mono-carboxylic acid chlorides such as benzoyl
chloride, C.sub.1-22 alkyl-substituted benzoyl chloride, toluoyl
chloride, bromobenzoyl chloride, cinnamoyl chloride, and
4-nadimidobenzoyl chloride, polycyclic, mono-carboxylic acid
chlorides such as trimellitic anhydride chloride, and naphthoyl
chloride, functionalized chlorides of aliphatic monocarboxylic
acids, such as acryloyl chloride and methacryoyl chloride, and
mono-chloroformates such as phenyl chloroformate, alkyl-substituted
phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene
chloroformate. Combinations of different end groups can be
used.
[0058] The endcapped polycarbonate can have a weight average
molecular weight (Mw) of 10,000 to 200,000 grams per mole (g/mol),
specifically 18,000 to 100,000 g/mol, as measured by gel permeation
chromatography (GPC), using a crosslinked styrene-divinylbenzene
column and calibrated to bisphenol A homopolycarbonate references.
GPC samples are prepared at a concentration of 1 mg per ml and are
eluted at a flow rate of 1.5 ml per minute.
[0059] The endcapped polycarbonate can have a melt volume flow rate
(MVR) of 2 to 300 cm.sup.3/10 min, 2 to 100 cm.sup.3/10 min, 2 to
30 cm.sup.3/10 min, using the ISO 1133 method, 2.16 kg load,
330.degree. C. temperature, 360 second dwell.
[0060] The endcapped polycarbonate can have at least one of lower
color, lower color after heat aging, or less plate-out after
molding compared to the same polycarbonate without the thioether
carbonyl endcaps.
[0061] Also provided are thermoplastic compositions including the
endcapped polycarbonate.
[0062] The thermoplastic composition can further include an impact
modifier. Examples of impact modifiers include natural rubber,
fluoroelastomers, ethylene-propylene rubber (EPR), ethylene-butene
rubber, ethylene-propylene-diene monomer rubber (EPDM), acrylate
rubbers, hydrogenated nitrile rubber (HNBR), silicone elastomers,
styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR),
styrene-(ethylene-butene)-styrene (SEBS),
acrylonitrile-butadiene-styrene (ABS),
acrylonitrile-ethylene-propylene-diene-styrene (AES),
styrene-isoprene-styrene (SIS),
styrene-(ethylene-propylene)-styrene (SEPS), methyl
methacrylate-butadiene-styrene (MBS), high rubber graft (HRG), and
the like.
[0063] An additive composition can be used, comprising one or more
additives selected to achieve a desired property, with the proviso
that the additive(s) are also selected so as to not significantly
adversely affect a desired property of the thermoplastic
composition. The additive composition or individual additives can
be mixed at a suitable time during the mixing of the components for
forming the composition. The additive can be soluble or non-soluble
in polycarbonate. The additive composition can include an impact
modifier, flow modifier, filler (e.g., a particulate
polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal),
reinforcing agent (e.g., glass fibers), antioxidant, heat
stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV
absorbing additive, plasticizer, lubricant, release agent (such as
a mold release agent), antistatic agent, anti-fog agent,
antimicrobial agent, colorant (e.g, a dye or pigment), surface
effect additive, radiation stabilizer, flame retardant, anti-drip
agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer
(TSAN)), or a combination comprising one or more of the foregoing.
For example, a combination of a heat stabilizer, mold release
agent, and ultraviolet light stabilizer can be used. In general,
the additives are used in the amounts generally known to be
effective. For example, the total amount of the additive
composition (other than any impact modifier, filler, or reinforcing
agent) can be 0.001 to 10.0 wt %, or 0.01 to 5 wt %, each based on
the total weight of the polymer in the composition.
[0064] In some aspects, the thermoplastic compositions can further
include a sulfonic acid stabilizer also referred to herein as an
"organosulfonic stabilizer". The organosulfonic stabilizer can be
an aryl or aliphatic sulfonic acid, including a polymer thereof, an
aryl or an aliphatic sulfonic acid anhydride, or an aryl or
aliphatic ester of an aryl or aliphatic sulfonic acid, or a polymer
thereof. In particular, the organosulfonic stabilizer is a
C.sub.1-30 alkyl sulfonic acid, a C.sub.6-30 aryl sulfonic acid, a
C.sub.7-30 alkylarylene sulfonic acid, a C.sub.7-30 arylalkylene
sulfonic acid, or an aromatic sulfonic acid polymer; an anhydride
of a C.sub.1-30 alkyl sulfonic acid, a C.sub.6-30 aryl sulfonic
acid, a C.sub.7-30 alkylarylene sulfonic acid, or a C.sub.7-30
arylalkylene sulfonic acid; or a C.sub.6-30 aryl ester of: a
C.sub.1-30 alkyl sulfonic acid, a C.sub.6-30 aryl sulfonic acid, a
C.sub.7-30 alkylarylene sulfonic acid, a C.sub.7-30 arylalkylene
sulfonic acid, or an aromatic sulfonic acid polymer; or a
C.sub.1-30 aliphatic ester of: a C.sub.1-30 alkyl sulfonic acid, a
C.sub.6-30 aryl sulfonic acid, a C.sub.7-30 alkylarylene sulfonic
acid, a C.sub.7-30 arylalkylene sulfonic acid, or an aromatic
sulfonic acid polymer. A combination of one or more of the
foregoing can be used.
[0065] In an aspect, the organosulfonic stabilizer is of formula
(8).
##STR00023##
In formula (8), R.sup.7 is each independently a C.sub.1-30 alkyl,
C.sub.6-30 aryl, C.sub.7-30 alkylarylene, C.sub.7-30 arylalkylene,
or a polymer unit derived from a C.sub.2-32 ethylenically
unsaturated aromatic sulfonic acid or its corresponding C.sub.1-32
alkyl ester. The C.sub.2-32 ethylenically unsaturated aromatic
sulfonic acid can be of the formula
##STR00024##
wherein R.sup.9 is hydrogen or methyl and R.sup.8 is as defined in
formula (8). Preferably the ethylenically unsaturated group and the
sulfonic acid or ester group are located para on the phenyl
ring.
[0066] Further in formula (8), R.sup.8 is hydrogen; or R.sup.8 is
C.sub.1-30 alkyl; or R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7. When R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7, each R.sup.7 in the compound of formula
(8) can be the same or different, but preferably each R.sup.7 is
the same.
[0067] In an aspect in formula (8), R.sup.7 is a C.sub.6-12 aryl,
C.sub.7-24 alkylarylene, or a polymer unit derived from a
C.sub.2-14 ethylenically unsaturated aromatic sulfonic acid or its
ester; and R.sup.8 is hydrogen, C.sub.1-24 alkyl, or a group of the
formula --S(.dbd.O).sub.2--R.sup.7 wherein R.sup.7 is a C.sub.6-12
aryl or C.sub.7-24 alkylarylene. In another aspect in formula (8),
R.sup.7 is a C.sub.7-10 alkylarylene or a polymer unit derived from
a C.sub.2-14 ethylenically unsaturated aromatic sulfonic acid, and
R.sup.8 is a hydrogen, C.sub.1-25 alkyl, or a group of the formula
--S(.dbd.O).sub.2--R.sup.7 wherein R.sup.7 is a C.sub.7-10
alkylarylene. In still another aspect, R.sup.7 is a C.sub.7-10
alkylarylene and R.sup.8 is a hydrogen or C.sub.1-6 alkyl. In still
another aspect, R.sup.7 is a C.sub.7-10 alkylarylene and R.sup.8 is
a hydrogen or C.sub.12-25 alkyl, or R.sup.8 is a C.sub.14-20 alkyl.
In another aspect, R.sup.7 is a polymer unit derived from a
C.sub.2-14 ethylenically unsaturated aromatic sulfonic acid,
preferably p-styrene sulfonic acid or para-methyl styrene sulfonic
acid, such that in formula (8) R.sup.8 is hydrogen.
[0068] The organosulfonic stabilizer can be a C.sub.1-10 alkyl
ester of a C.sub.7-12 alkylarylene sulfonic acid, preferably of
p-toluene sulfonic acid. More preferably the stabilizer is a
C.sub.1-6 alkyl ester of p-toluene sulfonic acid, such as butyl
tosylate. In another aspect, the organosulfonic stabilizer is an
anhydride of a C.sub.7-12 alkylarylene sulfonic acid, preferably
para-toluene sulfonic anhydride. In still another aspect, R.sup.7
is a C.sub.11-24 alkylarylene sulfonic acid, and R.sup.8 is
hydrogen. Alternatively, R.sup.7 is a C.sub.16-22 alkylarylene
sulfonic acid, and R.sup.8 is hydrogen.
[0069] When present, the amount of the organosulfonic stabilizer
used can be that amount effective to provide 2-40 ppm, or 2-20 ppm,
or 4-15 ppm, or 4-10 ppm, or 4-8 ppm of added sulfur, i.e.,
organosulfonic stabilizer-added sulfur, to the polycarbonates, each
based on parts by weight of the polycarbonate. When the
organosulfonic stabilizer is present, a lower amount of the
sulfur-containing, endcaps can be used to obtain the desired total
added sulfur content. When the organosulfonic stabilizer is
present, the total added sulfur content (the added sulfur from the
sulfur-containing endcaps and the organosulfonic stabilizer) can be
7-100 ppm, or 10-100 ppm, or 15-100 ppm, or 15-50 ppm, or 17-100
ppm, or 17-50 ppm, or 10-50 ppm, or 10-25 ppm, or 10-20 ppm, each
based on the total parts by weight of the polycarbonate.
[0070] The thermoplastic compositions can be manufactured by
various methods known in the art. For example, powdered
polycarbonate, and other optional components are first blended,
optionally with any fillers, in a high-speed mixer or by hand
mixing. The blend is then fed into the throat of a twin-screw
extruder via a hopper. Alternatively, at least one of the
components can be incorporated into the composition by feeding it
directly into the extruder at the throat or downstream through a
sidestuffer, or by being compounded into a masterbatch with a
desired polymer and fed into the extruder. The extruder is
generally operated at a temperature higher than that necessary to
cause the composition to flow. The extrudate can be immediately
quenched in a water bath and pelletized. The pellets so prepared
can be one-fourth inch long or less as desired. Such pellets can be
used for subsequent molding, shaping, or forming.
[0071] The molded sample of the endcapped polycarbonate can have a
haze of less than 10%, or less than 3% as measured according to
ASTM D1003-00, Procedure B, illuminant C, on a spectrophotometer,
at a thickness of 3.2 mm.
[0072] The molded sample of the endcapped polycarbonate can have a
visible transmission of greater than or equal to 70% as determined
according to ASTM D1003-00, Procedure A, using D65 illumination, 10
degrees observer, at a thickness of 3.2 mm.
[0073] The molded sample of the endcapped polycarbonate can have a
change in color of less than 0.5 unit lower than the change in
color of the control after heat aging.
[0074] The molded sample of the endcapped polycarbonate can have
lower color, less plate-out after molding, or a combination
thereof.
[0075] Shaped, formed, or molded articles comprising the
thermoplastic compositions are also provided. Compositions
comprising the endcapped polycarbonate can be molded into useful
shaped articles by a variety of methods, such as injection molding,
extrusion, rotational molding, blow molding, and thermoforming.
[0076] Exemplary articles include, for example, enclosures,
housings, panels, and parts for outdoor vehicles and devices;
enclosures for electrical and telecommunication devices; outdoor
furniture; aircraft components; boats and marine equipment,
including trim, enclosures, and housings; outboard motor housings;
depth finder housings; personal water-craft; jet-skis; pools; spas;
hot tubs; steps; step coverings; building and construction
applications such as glazing, roofs, windows, floors, decorative
window furnishings or treatments; treated glass covers for
pictures, paintings, posters, and like display items; wall panels,
and doors; counter tops; protected graphics; outdoor and indoor
signs; enclosures, housings, panels, and parts for automatic teller
machines (ATM); computer; desk-top computer; portable computer;
lap-top computer; hand held computer housings; monitor; printer;
keyboards; FAX machine; copier; telephone; phone bezels; mobile
phone; radio sender; radio receiver; enclosures, housings, panels,
and parts for lawn and garden tractors, lawn mowers, and tools,
including lawn and garden tools; window and door trim; sports
equipment and toys; enclosures, housings, panels, and parts for
snowmobiles; recreational vehicle panels and components; playground
equipment; shoe laces; articles made from plastic-wood
combinations; golf course markers; utility pit covers; light
fixtures; lighting appliances; network interface device housings;
transformer housings; air conditioner housings; cladding or seating
for public transportation; cladding or seating for trains, subways,
or buses; meter housings; antenna housings; cladding for satellite
dishes; coated helmets and personal protective equipment; coated
synthetic or natural textiles; coated painted articles; coated dyed
articles; coated fluorescent articles; coated foam articles; and
like applications.
[0077] The article can be a lens e.g., a camera lens, a sensor
lens, an illumination lens, a safety glass lens, an ophthalmic
corrective lens, or an imaging lens. The lens can be
hardcoated.
[0078] The article comprising the thermoplastic composition can be
a metallized article. The metallized article comprises, for
example, a substrate comprising the thermoplastic composition with
a metal layer disposed on the at least one side of the
substrate.
[0079] The substrate can be for example, a film. The substrate can
be made by molding the thermoplastic composition. The molding
methods are not particularly limited, and various known molding
methods can be listed, for example, injection molding, gas assist
injection molding, vacuum molding, extrusion, compression molding,
calendaring, rotary molding, etc. Of these, molding is usually
carried out by injection molding.
[0080] The metal layer can be disposed onto the surface of the
substrate with the aid of electrocoating deposition, physical vapor
deposition, or chemical vapor deposition or a suitable combination
of these methods. Sputtering processes can also be used. The metal
layer resulting from the metallizing process (e.g., by vapor
deposition) can be 0.001 to 50 micrometers (.mu.m) thick.
[0081] A base coat can be present between the substrate and the
metal layer. However, it is advantageous to form the metal layer
directly on the substrate surface without forming an undercoat. The
surfaces of the substrate are smooth and good gloss can be obtained
even by direct metal vapor deposition without treating the
substrate with primer. Moreover, the release properties of the
molded substrate during injection molding are good. Accordingly,
the surface properties of the molded substrate are superior without
replication of mold unevenness.
[0082] Chrome, nickel, aluminum, etc. can be listed as examples of
vaporizing metals. Aluminum vapor deposition is used in one aspect
as metal vapor deposition. The surface of the molded substrate can
be treated with plasma, cleaned, or degreased before vapor
deposition in order to increase adhesion.
[0083] The metallized article can have a protective layer disposed
on the metal layer. "Protective layer" refers for example, to a
layer which is made of a binder or a high molecular weight polymer
and formed on the outermost (e.g., the UV blocking) layer, so as to
exert the effects of preventing marring and improving mechanical
properties of the multilayer article. The protective layer can be
clear or pigmented and be formulated, for example, with
nitrocellulose or synthetic polymers configured to quickly dry by
evaporation without chemical reaction with the layer on which they
are disposed, providing a solid protective layer. The protective
coating material can further be thinned with alcohols. In certain
applications, the thickness of the protective layer is minimized.
The thickness of the protective layer can be, for example, 0.2
.mu.m or less.
[0084] The metallized articles can have little mold shrinkage, have
good surface gloss even when metal layers are directly vapor
deposited, and the vapor deposited surfaces do not become cloudy or
have rainbow patterns even on heating of the vapor deposited
surface. In particular, the metallized article can have no surface
defects visible to the eye.
[0085] Metallized articles have applications in optical reflectors
and can be used for automotive headlamps, headlight extensions, and
headlamp reflectors, for indoor illumination, for vehicle interior
illumination and for the like.
[0086] This disclosure is further illustrated by the following
non-limiting examples.
EXAMPLES
[0087] The materials used in the Examples are described in Table
1.
TABLE-US-00001 TABLE 1 Component Chemical Description Source PC-1
Linear bisphenol A polycarbonate, end SABIC capped with
p-cumylphenol (PCP), Mw = 29,000 g/mol as determined by GPC using
homopolycarbonate standards PC-2 Copolycarbonate of bisphenol A
(BPA) and Present bisphenol isophorone (4,4'-(3,3,5- disclosure
trimethylcyclohexane-1,1-diyl)diphenol or "BPI"), 80 mol % BPI, PCP
endcaps and optionally thioether carbonyl endcaps PC-3
Copolycarbonate of BPA and N- Present
phenylphenolphthaleinylbisphenol (PPPBP), disclosure 33 mol %
PPPBP, PCP endcaps and optionally thioether carbonyl endcaps PC-4
Copolycarbonate terpolymer comprising Present units derive from
BPA, BPI, and PPPBP, disclosure 20 mol % BPA, 70 mol % BPI, and 10
mol % PPPBP, PCP endcaps and optionally thioether carbonyl endcaps
BPA Bisphenol A, contains 1.5 ppm of sulfur Kumho/ Sumitomo BPI
Bisphenol isophorone, contains 4 ppm of SABIC sulfur PPPBP N-phenyl
phenolphthalein bisphenol SABIC PCP p-Cumylphenol Sigma- Aldrich
DLTDP Dilauryl 3,3'-thiodipropionate, CAS Reg. Sigma- No. 123-28-4
Aldrich DMP S-dodecyl-3-mercaptopropionic acid, CAS TCI Reg. No.
1462-52-8 PMP S-phenyl-3-mercaptopropionate, CAS Reg. Enamine No.
5219-65-8 Store Phosphite Tris(2,4-di-tert-butylphenyl)phosphite,
BASF Stabilizer obtained as IRGAPHOS 168 PETS Pentaerythritol
stearate Lonza
Testing Methods
[0088] Weight average molecular weight (Mw) determinations were
performed using GPC using a cross linked styrene-divinyl benzene
column, at a sample concentration of 1 milligram (mg) per
milliliter (mL), and as calibrated with bisphenol A
homopolycarbonate standards. Samples were eluted at a flow rate of
1.0 mL/min with methylene chloride as the eluent.
[0089] Glass transition temperature (Tg) was determined by
differential scanning calorimetry (DSC) according to ASTM D3418
with a 20.degree. C./min heating rate.
[0090] Melt volume rate (MVR) was determined according to ASTM
D1238-04 under the conditions listed in the Tables.
[0091] Yellowness index (YI) was determined according to ASTM D1925
on color chis having a thickness of 3.175 mm (0.125 inch).
[0092] Sulfur concentration was determined by oxidative combustion
microcoulometry of a solid sample at 1,100.degree. C. The vapors
emanating from the sample during the destruction were led through a
scrubber followed by a fluorescence detector with a flow of argon
and oxygen. Under these conditions, the sulfur was converted into
sulfur dioxide (SO.sub.2). The total sulfur concentration in the
sample was determined based on the response of the fluorescence
detector. Sulfur quantification was performed using a Thermo
Euroglass ECS3000 analyzer with a TS-UV module (Thermo Fisher
Scientific).
Example 1
[0093] A model system was used to first establish the stability and
usefulness of the sulfur stabilizers. Accordingly, a BPA
polycarbonate (PC-1) was formulated with different levels of
dilauryl thiodipropionate (DLTDP) as blends 1-A to 1-F as shown in
Table 2. The amount of each additive is based on 100 wt % of the
polycarbonate.
TABLE-US-00002 TABLE 2 Ex. No. Units 1-A 1-B 1-C 1-D 1-E 1-F Added
sulfur level ppm 0 5 10 5 30 0 from DLTDP PC-1 wt % 100 100 100 100
100 100 PS wt % 0.1 0.1 0.1 0.1 0.1 0.1 PETS wt % 0.04 0.04 0.04
0.04 0.04 0.04 DLTDP wt % 0 0.008 0.016 0.008 0.048 MVR 330.degree.
C., cm.sup.3/ 26.1 25 25.9 26.9 27.4 25.4 360 sec, 2.16 kg 10 min
MVR 330.degree. C., cm.sup.3/ 28.3 27.8 27.5 27.8 27.9 27.7 1080
sec, 2.16 kg 10 min MVR shift after 6 to % -8.43 -11.20 -6.18 -3.35
-1.82 -9.06 10 min dwell
[0094] The blends in Table 2 were extruded on a twin-screw extruder
and molded at 316.degree. C. for 35 seconds (standard) or
338.degree. C. for 60 seconds (abusive). Table 2 shows that there
is no significant loss in melt stability with increasing sulfur
level relative to the baseline (1-A). FIG. 1 shows that as-molded
YI decreases with increasing sulfur level. In addition, as the
sulfur level increases to 10 ppm or greater, there is little
difference in melt stability between the abusive and normal
conditions. FIG. 2 shows that the sample with 30 ppm of sulfur
exhibited substantially no change in YI with increasing
temperature, whereas the YI of the sample without the sulfur
stabilizer increased significantly with increasing molding
temperature.
Examples 2 to 5
[0095] Samples were prepared containing PC-2 (Example 2), PC-2 with
DMP as a thioether carbonyl endcapping agent (Examples 3 and 4),
and PC-2 with PMP as a thioether carbonyl endcapping agent (Example
5).
[0096] Example 2 was prepared as follows. 6.0 g (26.3 mmol) of BPA,
32.6 g (105.1 mmol) of BPI, and 1.12 g (5.3 mmol) of PCP were
suspended in 300 mL of deionized water and 500 mL of
dichloromethane. 370 .mu.L (2.6 mmol) of triethylamine was then
added thereto. The mixture was mechanically stirred for 5 minutes
(min). To start polymerization, phosgene was bubbled into the
mixture at a rate of 1 g/min for 18 min. To this, a caustic aqueous
solution (33 wt %) was added to maintain the pH at 9.5. After the
reaction, phosgene was purged with nitrogen for 15-20 min. The
phases were then separated, and the organic layer was washed with
1.times.500 mL of 0.1 molar (M) HCl. After that, the
dichloromethane phase was washed with 5 x 500 mL deionized water
and the resulting copolymer PC-1 was precipitated by pouring the
organic phase on hot water with mechanical stirring.
[0097] Example 3 was prepared in the same way as Example 2, except
2 mg of DMP (6 ppm of added sulfur) was added to the mixture prior
to the introduction of phosgene. To start polymerization, phosgene
was bubbled into the mixture at a rate of 1 g/min for 18 min. To
this, a caustic aqueous solution (33 wt %) was added to maintain
the pH at 5 for the first 5 min, and then the caustic addition rate
was adjusted to achieve a target pH of 9.5. After the reaction,
phosgene was purged with nitrogen and the product was obtained
using the same workup as Example 2.
[0098] For Example 4, PC-2 with DMP as a thioether carbonyl
endcapping agent (73 ppm of added sulfur) was prepared in the same
manner as Example 3, except 24.5 mg of DMP was used. For Example 5,
PC-2 with PMP as a thioether carbonyl endcapping agent (73 ppm of
added sulfur) was prepared in the same manner as Example 3, except
23 mg of PMP was used instead of DMP.
[0099] Table 3 shows the properties for Examples 2 to 5.
TABLE-US-00003 TABLE 3 Sulfur Mw Mw/ [S] Charged [S] Found Tg
Example End Cap (g/mol) Mn (ppm) (ppm) (.degree. C.) 2 None 24,028
3.94 0 7 216 3 DMP 21,506 3.51 6 15 216 4 DMP 22,067 3.65 73 98 216
5 PMP 22,733 3.15 73 133 213
[0100] As seen in Table 3, thioether carbonyl endcapping agents
(DMP and PMP) resulted in formation of thioether carbonyl endcaps
in the resulting polycarbonates, as shown by the increase in sulfur
content in the polycarbonate when compared with the control
(Example 2).
Example 6
[0101] PC-3 was prepared as follows. 42.1 g (184 mmol) of BPA, 31.7
g (79.0 mmol) of PPPBP, and 2.45 g (11.5 mmol) of PCP were
suspended in 300 mL of deionized water and 500 mL of
dichloromethane. To this, 0.73 g (5.3 mmol) of triethylamine was
added. The mixture was mechanically stirred for 5 min. To start
polymerization, phosgene was bubbled into the mixture at a rate of
1 g/min for 35 min and the pH was regulated to 5 for the first 5
min, then the caustic addition rate was adjusted to achieve a
target pH of 9.5 to 10 using aqueous caustic (33 wt %). After the
reaction, phosgene was purged with nitrogen for 15-20 min. The
phases were separated, and the organic layer was washed with
1.times.500 mL of 0.1 M HCl. After that, the dichloromethane phase
was washed with 4.times.500 mL deionized water and the copolymer
was precipitated by pouring the organic phase on hot water with
mechanical stirring.
Example 7
[0102] PC-3 with DMP as a thioether carbonyl endcapping agent (5
ppm of added sulfur) was prepared in the same manner as Example 6,
except the mixture further included 3.4 mg of DMP.
Example 8
[0103] PC-4 terpolymer was prepared as follows. 10.56 g (46.3 mmol)
of BPA, 50.33 g (162.1 mmol) of BPI, and 2.46 g (11.6 mmol) of PCP
were suspended in 265 mL of deionized water and 500 mL of
dichloromethane. To this, 0.65 mL (4.6 mmol) of triethylamine was
added. The mixture was mechanically stirred for 5 min. To start
polymerization, phosgene was bubbled into the mixture at a rate of
1 g/min for 30.5 min and the pH was regulated to 5 for the first 5
min, then the caustic addition rate was adjusted to achieve a
target pH of 9.5 to 10 using aqueous caustic (33 wt %).
Concurrently, a solution containing 9.11 g (23.2 mmol) of PPPBP,
5.8 g of caustic aqueous solution (33 wt %), and 20 g of water was
added to the mixture over the first 12 min. After the reaction,
phosgene was purged with nitrogen for 15-20 min. The phases were
separated, and the organic layer was washed with 1.times.500 mL of
0.1 M HCl. Then, the dichloromethane phase was washed with
4.times.500 mL deionized water and the terpolymer was precipitated
by pouring the organic phase on hot water with mechanical
stirring.
Example 9
[0104] PC-4 terpolymer with DMP as a thioether carbonyl endcapping
agent (6 ppm of added sulfur) was prepared in the same manner as
Example 8, except the mixture further included 3.2 mg of DMP.
[0105] Table 4 shows the properties for Examples 6 to 9.
TABLE-US-00004 TABLE 4 [S] PPPBP/BPI/BPA Charged Example (molar
ratio) Sulfur End Cap Mw (g/mol) (ppm) 6 30/0/70 None 21,000 0 7
30/0/70 DMP 21,000 5 8 10/70/20 None 22,000 0 9 10/70/20 DMP 22,000
6
Examples 10 to 12
[0106] Samples were prepared of PC-2 (Example 10), PC-2 containing
12 ppm of added sulfur from DMP (Example 11), or 36 ppm (Example
12) of added sulfur from DMP.
[0107] Example 10 was prepared as follows. To a mixture of 22 L of
methylene chloride, 9 L of deionized water, 715.1 g of BPA (3.132
mol), 3890 of BPI (12.53 mol), 144.3 g of PCP (0.6798 mol, 4.34 mol
%), 29 g of triethylamine (1.9 mol %), and 10 g of sodium gluconate
in a 75-L reactor equipped with mechanical stirring, recirculation
line with pH probe, subsurface phosgene addition, chilled glycol
condenser, caustic scrubber for the exit gas, and caustic solution
inlet was added 2360 g of phosgene (23.83 mol) at a rate of 80
g/min. Aqueous caustic (33 wt %) was added to maintain a pH of 8-9
in the reactor. After completion of the reaction, the reactor was
then purged with nitrogen to remove any free phosgene. The batch
was transferred to a 100-L work-up tank. The batch was purified on
a centrifuge train where the brine phase was separated and the
resin solution in methylene chloride was extracted with aqueous
HCl, and then as washed with deionized water until titratable
chlorides were less than 5 ppm. The methylene chloride solution was
then steam-precipitated, and the polymer dried under hot nitrogen
until volatile levels were less than 0.4 wt %.
[0108] PC-2 containing 12 ppm (Example 11) or 36 ppm (Example 12)
of added sulfur from DMP were prepared in the same manner as
Example 10, except an appropriate amount of DMP was added prior to
phosgenation. 2360 g of phosgene (23.83 mol) was introduced at a
rate of 80 g/min. Aqueous caustic (33 wt %) was added to maintain a
pH of 5 to 7 in the reactor for 10 min, after which time the pH was
adjusted to 9-10. After completion of the reaction, the reactor was
then purged with nitrogen to remove any free phosgene. Workup and
purification was the same as for Example 10.
[0109] The copolymers of Examples 10 to 12 were dry blended with
0.1 wt % of phosphite stabilizer and 0.04 wt % of PETS and mixed in
a paint shaker. The blends were extruded on 26 mm twin-screw
extruder having vacuum venting with barrel temperatures set points
ramped from 177 to 293.degree. C. (feed to die throat) and a screw
speed of 850 rpm. The extrudate was cooled in a water bath and then
chopped into pellets for testing and molding.
[0110] A 180-ton injection molding machine with a 0.1488 kg barrel
was used to mold color plaques having a thickness of 3.175 mm. The
copolymer blends were molded at 316.degree. C. for 35 seconds
(standard) or 338.degree. C. for 60 seconds (abusive).
Examples 13 to 17
[0111] Samples of PC-4 with DMP as a thioether carbonyl endcapping
agent were prepared using an interfacial process to provide PC-4
having an added sulfur content of 0 ppm (Example 13), 12 ppm
(Example 14), and 36 ppm (Example 15).
[0112] Examples 13 to 15 were prepared as follows. In an exemplary
process, PPP-BPI-BPA (10/70/20) with 12 ppm of added sulfur
(Example 14) was prepared as follows. To a mixture of 22 L of
methylene chloride, 9 L of deionized water, 686.5 g of BPA (3.007
mol), 3267 g of BPI (10.53 mol), 591.5 g of PPPBP (1.504 mol), 0.51
g DMP (1.9 mmol), 139.8 g of p-cumylphenol (0.659 mol), 25 mL of
triethylamine, and 10 g of sodium gluconate in a 75 L reactor
equipped with mechanical stirring, recirculation line with pH
probe, subsurface phosgene addition, chilled glycol condenser,
caustic scrubber for exit gas, and caustic solution inlet was added
2200 g of phosgene at a rate of 70 g/min. Aqueous caustic (33 wt %)
was added as needed to maintain pH of 5 to 8 for the first 10 min.
Then the caustic addition was adjusted to target a pH of 9 to 9.5
in the reactor. After the phosgene was added, the reactor was then
purged with nitrogen. A sample was obtained for GPC analysis. An
additional 200 g of phosgene was added, and the Mw was determined.
The process was repeated until the MW increase was less than 200
g/mol. The polymer mixture was transferred to the 100 L work-up
tank and purified on a centrifuge train where the brine phase was
separated and the polymer solution in methylene chloride was
extracted with aqueous HCl and then washed with deionized water
until titratable chlorides were less than 5 ppm. The polymer
solution was then steam-precipitated, and the resultant polymer
dried under hot nitrogen until volatile levels were <0.4 wt
%.
[0113] The same procedure as Example 14 was followed, except the
ratio of PPPBP-BPI-BPA was 15/65/20 (Example 16) or 20/65/17
(Example 17). Table 5 provides properties for terpolymers of
Examples 14, 16, and 17.
TABLE-US-00005 TABLE 5 PPPBP/BPI/BPA ratio Mw (g/mol) Tg (.degree.
C.) Example 14 10/70/20 22,500 215 Example 16 15/65/20 22,500 215
Example 17 20/65/17 22,500 225
[0114] The copolymers of Examples 13 to 15 were dry blended with
0.1 wt % of phosphite stabilizer and 0.04 wt % of PETS, mixed in a
paint shaker, and then extruded and molded using the same
conditions as for Examples 10 to 12.
[0115] The disclosure is further illustrated by the following
non-limiting aspects.
[0116] Aspect 1. An endcapped polycarbonate, comprising thioether
carbonyl endcaps of the formula --C(.dbd.O)-L-S--R, wherein L is a
C.sub.1-12 aliphatic or aromatic linking group, and R is a
C.sub.1-20 alkyl, C.sub.6-18 aryl, or C.sub.7-24 arylalkylene.
[0117] Aspect 2. The endcapped polycarbonate of Aspect 1, wherein
the thioether carbonyl endcaps are of the formula
##STR00025##
or a combination thereof, wherein R is a C.sub.1-20 alkyl,
C.sub.6-18 aryl, or C.sub.7-24 arylalkylene, preferably a
C.sub.1-14 alkyl, C.sub.6-12 aryl, or a C.sub.7-13 arylalkylene,
and b is 1 to 5, preferably 1 to 2.
[0118] Aspect 3. The endcapped polycarbonate of Aspect 1 or 2,
wherein the thioether carbonyl endcaps are of the formula
##STR00026##
or a combination thereof.
[0119] Aspect 4. The endcapped polycarbonate of any one or more of
the preceding Aspects, wherein the thioether carbonyl endcaps are
present in an amount effective to provide 3 to 80 parts per million
by weight, preferably 3 to 70 parts per million by weight, or 5 to
50 parts per million by weight, or 10 to 50 parts per million by
weight of added sulfur, based on the total parts by weight of the
endcapped polycarbonate; or having a total sulfur content of 3 to
150 parts per million by weight, preferably 3 to 100 parts per
million by weight, or 3 to 70 parts per million by weight, or 5 to
50 parts per million by weight, or 10 to 50 parts per million by
weight, based on the total parts by weight of the endcapped
polycarbonate; or both.
[0120] Aspect 5. The endcapped polycarbonate of any one or more of
the preceding Aspects, comprising a polycarbonate homopolymer, a
copolycarbonate, a poly(ester-carbonate), a
poly(carbonate-siloxane), a poly(ester-carbonate-siloxane)
terpolymer, or a combination thereof; preferably comprising a
copolycarbonate; more preferably a high heat copolycarbonate having
a Tg of 170.degree. C. or higher.
[0121] Aspect 6. The endcapped polycarbonate of any one or more of
the preceding Aspects, wherein the polycarbonate comprises: 0 to 95
mol %, preferably 5 to 90 mol %, more preferably 15 to 80 mol % of
low heat aromatic dihydroxy monomer groups; and 5 to 100 mol %,
preferably 10 to 95 mol %, more preferably 20 to 85 mol % of high
heat aromatic dihydroxy monomer groups.
[0122] Aspect 7. The endcapped polycarbonate of Aspect 7, wherein
the low heat aromatic dihydroxy monomer groups are bisphenol A
groups, and the high heat aromatic dihydroxy monomer groups are of
formula (9a-2), (10a-2), or a combination thereof; preferably
wherein the high heat aromatic dihydroxy monomer groups are
2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine (PPPBP),
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (BPI), or a
combination thereof.
[0123] Aspect 8. The endcapped polycarbonate of any one or more of
the preceding Aspects wherein, compared to the same polycarbonate
without the thioether carbonyl endcaps, the endcapped polycarbonate
has at least one of lower color, lower color after heat aging, or
less plate-out after molding.
[0124] Aspect 9. The endcapped polycarbonate of any one or more of
the preceding Aspects, wherein a molded sample of the endcapped
polycarbonate has at least one of a haze of less than 10%, or less
than 3% as measured according to ASTM D1003-00, Procedure B,
illuminant C, on a spectrophotometer, at a thickness of 3.2 mm; a
visible transmission of greater than or equal to 70% as determined
according to ASTM D1003-00, Procedure A, using D65 illumination, 10
degrees observer, at a thickness of 3.2 mm.
[0125] Aspect 10. A method for the manufacture of the endcapped
polycarbonate of any one or more of the preceding Aspects, the
method comprising reacting a thioether carbonyl endcapping agent of
formula (A) during manufacturing the polycarbonate from a
bisphenol.
[0126] Aspect 11. The method of Aspect 10, wherein the
manufacturing is by interfacial polymerization, and G.sub.L is a
hydroxy group, a salt of a hydroxy group, or a halide.
[0127] Aspect 12. The method of Aspect 10, wherein the
manufacturing is in the melt, and G is a hydroxy group or a salt of
a hydroxy group.
[0128] Aspect 13. The method of Aspect 10, comprising combining the
thioether carbonyl endcapping agent with the bisphenol, wherein the
combining is: during manufacturing of the bisphenol, during
dissolution of the bisphenol before manufacturing the
polycarbonate, at the same time that the bisphenol is added to a
reaction mixture to form the polycarbonate, during phosgenation to
form the polycarbonate, before shipping the bisphenol, or before
storing the bisphenol.
[0129] Aspect 14. A method of manufacturing an article comprising
the endcapped polycarbonate of any of one or more of Aspects 1 to
9, preferably wherein the manufacturing comprises injection molding
or extruding the endcapped polycarbonate.
[0130] Aspect 15. An article comprising the endcapped polycarbonate
of any of one or more of Aspects 1 to 9, preferably wherein the
article is a molded article, an extruded layer, or an extruded
fiber.
[0131] The compositions, methods, and articles disclosed herein can
alternatively comprise, consist of, or consist essentially of, any
appropriate components or steps herein disclosed. The compositions,
methods, and articles can additionally, or alternatively, be
formulated so as to be devoid, or substantially free, of any steps,
components, materials, ingredients, adjuvants, or species that are
otherwise not necessary to the achievement of the function and/or
objectives of the compositions, methods, and articles.
[0132] The singular forms "a", "an", and "the" include plural
referents unless the context clearly dictates otherwise.
"Combinations" is inclusive of blends, mixtures, alloys, reaction
products, and the like. "Or" means "and/or" unless clearly
indicated otherwise by context. Reference to "an aspect" means that
a particular element described in connection with the aspect is
included in at least one aspect described herein and may or may not
be present in other aspects. A "combination thereof" is open and
includes any combination comprising at least one of the listed
elements, optionally together with a like or equivalent element not
listed. The described elements may be combined in any suitable
manner in the various aspects.
[0133] The endpoints of all ranges directed to the same component
or property are inclusive and independently combinable Disclosure
of a narrower range or more specific group in addition to a broader
range is not a disclaimer of the broader range or larger group.
[0134] As used herein, the term "alkyl" means a straight or
branched chain, saturated monovalent hydrocarbon group; "alkylene"
means a straight or branched chain, saturated, divalent hydrocarbon
group; "alkylidene" means a straight or branched chain, saturated
divalent hydrocarbon group, with both valences on a single common
carbon atom; "alkenyl" means a straight or branched chain
monovalent hydrocarbon group having at least two carbons joined by
a carbon-carbon double bond; "cycloalkyl" means a non-aromatic
monovalent monocyclic or multicyclic hydrocarbon group having at
least three carbon atoms, "aryl" means an aromatic monovalent group
containing only carbon in the aromatic ring or rings; "arylene"
means an aromatic divalent group containing only carbon in the
aromatic ring or rings; "alkylarylene" means an aryl group
substituted with an alkyl group, where 4-methylphenyl is an
exemplary alkylarylene group; "arylalkylene" means an alkylene
group substituted with an aryl group, where benzyl is an exemplary
arylalkylene group; "alkoxy" means an alkyl group substituted with
the indicated number of carbon atoms attached through an oxygen
bridge (--O--); and "aryloxy" means an aryl group as defined above
with the indicated number of carbon atoms attached through an
oxygen bridge (--O--).
[0135] Unless otherwise indicated, each of the foregoing groups can
be unsubstituted or substituted, provided that the substitution
does not significantly adversely affect synthesis, stability, or
use of the compound. The term "substituted" means that at least one
hydrogen on the designated atom or group is replaced with another
group, provided that the designated atom's normal valence is not
exceeded. When the substituent is oxo (i.e., .dbd.O), then two
hydrogens on the atom are replaced. Combinations of substituents or
variables are permissible provided that the substitutions do not
significantly adversely affect synthesis or use of the compound.
Exemplary groups that can be present on a "substituted" position
include but are not limited to cyano; hydroxyl; nitro; azido;
alkanoyl (e.g., a C.sub.2-6 alkanoyl group such as acyl
(H.sub.3CC(.dbd.O)--)); carboxamido; C.sub.1-6 or C.sub.1-3 alkyl,
cycloalkyl, alkenyl, and alkynyl (including groups having at least
one unsaturated linkages and from 2 to 8, or 2 to 6 carbon atoms);
C.sub.1-6 or C.sub.1-3 alkoxys; C.sub.6-10 aryloxy such as phenoxy;
C.sub.1-6 alkylthio; C.sub.1-6 or C.sub.1-3 alkylsulfinyl;
C.sub.1-6 or C.sub.1-3 alkylsulfonyl; aminodi(C.sub.1-6 or
C.sub.1-3)alkyl; C.sub.6-12 aryl having at least one aromatic rings
(e.g., phenyl, biphenyl, naphthyl, or the like, each ring either
substituted or unsubstituted aromatic); C.sub.7-19 arylalkylene
having 1 to 3 separate or fused rings and from 6 to 18 ring carbon
atoms; or arylalkyleneoxy having 1 to 3 separate or fused rings and
from 6 to 18 ring carbon atoms, with benzyloxy being an exemplary
arylalkyleneoxy. The stated number of carbon atoms includes any
substituents.
[0136] Unless specified to the contrary herein, all test standards
are the most recent standard in effect as of the filing date of
this application, or, if priority is claimed, the filing date of
the earliest priority application in which the test standard
appears. Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this invention belongs. All cited
patents, patent applications, and other references are incorporated
herein by reference in their entirety.
[0137] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or may be presently unforeseen may
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they may be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *